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This paper addresses the modelling of cesium sorption in non-equilibrium and nonlinear conditions with a two-site model. Compared to the classical K d approach, the proposed model better reproduced the breakthrough curves observed during continuous-flow stirred tank reactor experiments conducted on two contrasted soils. Fitted parameters suggested contrasted conditions of cesium sorption between 1) equilibrium sites, with low affinity and high sorption capacity comparable to CEC and 2) non-equilibrium sites, with a fast sorption rate (half-time of 0.2-0.3 h), a slow desorption rate (half-time of 3-9 days) and a very low sorption capacity (0.02-0.04% of CEC). Comparison of EK sites densities with sorption capacities derived from the literature suggests that the EK equilibrium and kinetic sites might correspond to ion exchange and surface complexation of soil clay minerals respectively. This work stresses the limits of the K d model to predict 137 Cs sorption in reactive transport conditions and supports an alternative non-equilibrium nonlinear approach., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Laurent Garcia-Sanchez reports financial support was provided by Electricité de France., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (L Cy,Pr )H 2 , of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2-11 by potentiometry and visible absorption spectrophotometry. Equilibrium constants and absorption spectra for three [UO 2 (DFB)H h ] (h-1)+ (h = 1-3) and five [UO 2 (L Cy,Pr ) l H h ] (2+h-2l)+ (-1 ≤ h ≤ 1 for l = 1 and h = 0-1 for l = 2) solution complexes were determined at 25.0 °C and I = 0.1 M KNO 3 . Similar studies for the Fe 3+ /(L Cy,Pr ) 2- system revealed the formation of five species having [Fe(L Cy,Pr )] + , [Fe(L Cy,Pr )OH], [Fe(L Cy,Pr )(OH) 2 ] - , [Fe(L Cy,Pr ) 2 H], and [Fe 2 (L Cy,Pr ) 3 ] compositions. Then, the ability of DFB, (L Cy,Pr )H 2 , and citrate to solubilize either U or Pu from pitchblende-rich soils (soils 1 and 2) or freshly plutonium-contaminated soils (LBS and PG) was evaluated by performing batch extraction tests. U was extracted significantly only by citrate after a day. After one week, the amount of U complexed by citrate only slightly exceeded that measured for the siderochelates, following the order citrate > (L Cy,Pr )H 2  ≥ DFB ≈ H 2 O, and were comparatively very low. Pu was also more efficiently extracted by citrate than by DFB after a day, but only by a factor of ~2-3 for the PG soil, while the Pu concentration in the supernatant after one week was approximately the same for both natural chelators. It remained nearly constant for DFB between the 1st and 7th day, but drastically decreased in the case of citrate, suggesting chemical decomposition in the latter case. For the Fe-rich soils 1 and 2, the efficiencies of the three chelators to solubilize Fe after a day were of the same order of magnitude, decreasing in the order DFB > citrate > (L Cy,Pr )H 2 . However, after a week DFB had extracted ~1.5 times more Fe, whereas the amount extracted by the other chelators stayed constant. For the less Fe-rich LBS and PG soils contaminated by Pu, the amounts of extracted Fe were higher, especially after 7 days, and the DFB outperformed citrate by a factor of nearly 3. The higher capacity of the hexadentate DFB to extract Pu in the presence of Fe and its lower ability to mobilize U qualitatively agree with the respective complexation constant ratios, keeping in mind that both Pu-containing soils had a lower iron loading. Noticeably, (L Cy,Pr )H 2 has roughly the same capacity as DFB to solubilize U, but it mobilizes less Fe than the hexadentate siderophore. Similarly, citrate has the highest capacity to extract Pu, but the lowest to extract Fe. Therefore, compared to DFB, (L Cy,Pr )H 2 shows a better U/Fe extraction selectivity and citrate shows a better Pu/Fe selectivity., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Mechanisms of uranium (U) transfer from soil to plants remain poorly understood. The kinetics of supply of U to the soil solution from solid phases could be a key point to understand its phytoavailability and implications for environmental risk assessment. Root activity, particularly the continuous release of organic acids in the rhizosphere, could have an effect on this supply. We tested the impact of citrate exudation by roots of Lupinus albus, either P-sufficient (P+) or P-deficient (P-), on the phytoavailability of U from a naturally contaminated soil (total content of 413 mg U kg -1 ) using a rhizotest design. Combined effects of P (P-/P+ used to modulate plant physiology) and citrate (model exudate) on the solubilization of U contained in the soils were tested in closed reactors (batch). The batch experiment showed the existence of a low U available pool (0.4% total U) and high accessibility (k d ' around 20 L kg -1 ) which was not significantly affected by P treatment or citrate concentrations. Analysis of U, Fe, Ca, P and citrate concentrations in the batches suggested a complex combination of mechanisms and factors including desorption, resorption, precipitation, co-sorption. On rhizotest, L. albus plants extracted 0.5-0.75% of the total U and between 25 and 40% of the estimated available U present in the rhizotest in 5 days. Uranium accumulation at the whole plant level (20 mg U kg -1 d.w. , shoot to root ratio around 10 -3 ) seemed to be dependent neither on the plant P nutrition status nor citrate exudation level, possibly in relation with the equivalent accessibility of U whatever the growth conditions. Yet differential translocation to shoots seemed to be positively correlated to citrate exudation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Phosphate (P) is an essential element for plant development but is generally present in limiting amount in the soil solution. Plant species have developed different mechanisms promoting the solubilization of this element in soils to ensure a sufficient supply for their growth. One of these mechanisms is based on the ability of certain species such as L. albus to exude large amounts of citrate through specific tertiary roots called cluster-roots. Uranium (U) is an ubiquitous contaminant known firstly for its chemical toxicity and secondly for its high affinity for P with which it forms low-soluble complexes in soils. We highlight the effects of P-U interaction on the physiology of L. albus and particularly on citrate exudation, and the impact of this root process on the phytoavailability of U and its accumulation in plants in a hydroponic study. Different levels of P (1 and 100 μM) and U (0 and 20 μM) have been tested. Our results show no toxicity of U on the development of L. albus with an adequate P supply, whereas the effects of P starvation are amplified by the presence of U in the growth medium, except for the production of cluster-roots. Citrate exudation is totally inhibited by U in a low-P environment whereas it increases in the presence of U when its toxicity is lowered by the addition of P. The differences observed in terms of toxicity and accumulation are partly explained by the microphotographs obtained by electron microscopy (TEM-EDX): in the absence of P, U penetrates deep into the roots and causes lethal damages, whereas in presence of P, we observe the formation of U-P complexes which limit the internalization of the pollutant and so its toxicity., (Copyright © 2013 Elsevier Ltd. All rights reserved.)